JPH062579B2 - Hydrophobic crystalline microporous siliceous materials of regular geometric shape - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to regularly geometrically shaped hydrophobic crystalline microporous siliceous materials and processes for their preparation.

BACKGROUND OF THE INVENTION Crystalline hydrated aluminous tectosilicates of Group I and II elements such as potassium, sodium, magnesium and calcium are naturally occurring or can be synthesized in the laboratory and have higher polyvalent ions such as rare earths. Is
It is easily introduced by cation exchange. The structure, these tectosilicates are aluminas "framework" silicates which are based on AlO ₄ and SiO ₄ tetrahedra infinitely extending three-dimensional network coupled to each other by sharing of oxygen ions. Such frameworks or lattices carry a net negative charge and are diagrammatically of the general structural formula Where M + is a cation, such as sodium or potassium, and m is equal to the number of negatively charged aluminum ions in the lattice. Aluminous tectosilicate is an experimental unit lattice formula M _{x / n} [(AlO ₂ ) _x (SiO ₂ ) _y ] .wH ₂ O (where M is a cation having a valence of n and w is water). It is the number of molecules, and the y / x ratio is usually about 1-20 depending on the structure of the particular tectosilicate being surrounded). The sum (x + y) is the total number of tetrahedra in the unit cell; the portion in square brackets represents the tectosilicate framework composition.

After dehydration, some tectosilicates exhibit a large internal surface area available for absorbing liquids or gases due to the clearing of channels and pores. The channels evenly penetrate the entire volume of solids. The outer surface of the tectosilicate represents only a small part of its total effective surface area.
Therefore, dehydrated tectosilicates will selectively sorb or reject different molecules based on their effective molecular size and shape. This size-selective sorption effect can be total or partial. Overall, diffusion of the first kind into the solid can be prevented at all, while diffusion of the second kind occurs. In part, the components of the binary mixture can diffuse into the solid at different rates depending on the exposure conditions involved.

Due to the point charge on the surface of the aluminous tectosilicate pores, highly polar molecules such as water, ammonia, alcohols, etc. are generally sorbed more strongly than less polar molecules such as hydrocarbons or inert gases. Water is easily sorbed and tightly bound by the aluminous tectosilicate. Water molecules have a strong tendency to cluster within the diamond-like lattice fragments in both the liquid and vapor phases. This hydrophilicity has been used to remove water in either the liquid or gas phase from mixtures of water with molecules such as hydrocarbons processed by the petroleum industry. Gas streams containing small amounts of readily sorbed gas molecules, such as nitrogen, hydrogen, etc., can also be dried with dehydrated tectosilicate due to the extremely strong attraction of tectosilicate to water.

However, the hydrophilic nature of aluminous tectosilicates prevents their use in selectively removing less polar materials from water-containing mixtures. For example, tectosilicates, which will remove significant amounts of dissolved ammonium from human excreta, will find utility in diapers or bed pads. In diapers or bed pads, tectosilicates will act to prevent ammonia burn, at least in part, and thus prevent ammonia dermatitis (diaper rash). Such materials would also be useful as ingredients in litters such as those used to sorb excrement of farm animals or domestic pets.
Both naturally occurring and synthetic tectosilicates have been used to remove nitrogenous constituents from liquid human and animal wastes by ion exchange, but in the presence of large amounts of water they remove dissolved ammonia. The problem has not been resolved. See U.S. Pat. No. 3,935,363 to Valholder. The preferential sorption of water molecules over ammonia molecules rapidly reduces the ability of tectosilicates to sorb ammonia.

The desirability of removing carbon monoxide from cigarette smoke while leaving large flavoring molecules in the smoke using tectosilicate as a sorbent has long been recognized.
However, the realization of this goal has actually failed due to the preferential sorption of water vapor, which is also a constituent of tobacco smoke and rapidly fills the tectosilicate pores, thereby impeding the sorption of significant amounts of carbon monoxide. There is. One attempt to prevent this occlusion is US Pat. No. 3,658,06.
Includes the use of a water-absorbing material placed in the smoke stream upstream from the tectosilicate as disclosed in US Pat. Metal catalysts are also introduced into the tectosilicates to oxidize, for example, carbon monoxide to carbon dioxide or catalyze the hydrogenation and cracking of petroleum feedstocks. Such a catalyst-supporting tectosilicate is also susceptible to deactivation by water and catalyst poisoning through pore occlusion. For example, British Patent No. 2,
See 013,476A.

Hydrophobic tectosilicate materials will overcome these poisoning and occlusion problems by being resistant to water sorption while maintaining affinity and activity for other molecular species. Such hydrophobic tectosilicates would be useful in removing impurities from aqueous feedstocks as well as protecting introduced catalysts from water deactivation.

DISCLOSURE OF THE INVENTION It is therefore an object of the present invention to provide a hydrophobic tectosilicate based material which resists water sorption while retaining a useful affinity for other molecules.

Another object of the present invention is to provide a material based on a hydrophobic tectosilicate that will strongly sorb ammonia while exhibiting a reduced hydrophilicity, preferably less than that of the material that absorbs ammonia. To provide.

It is an object of the present invention to remove a substantial portion of the aluminum from the lattice points of naturally occurring or synthetic aluminous tectosilicates so that reactive lattice points, preferably the general structure, within the siliceous lattice of tectosilicates. Is achieved by a hydrophobic tectosilicate produced by a reaction process involving making a hydroxyl-containing nest of The resulting aluminum-deficient tectosilicate is dehydrated, for example, by heating to drive out the water of hydration without destroying the reaction sites or otherwise deactivating. The resulting material is then derivatized to replace the hydroxyl groups with a predetermined moiety (the moiety is aluminum or preferably a weaker point power source than the hydroxyl group). The selection of suitable dealumination, dehydration and derivatization conditions in accordance with the present invention results in a novel class of microporous crystalline or otherwise having a stronger affinity for ammonia than for water under equivalent exposure conditions. This produces a hydrophobic substance.

The term "weaker point source" as used herein with respect to substituents means that it has a lower total charge and / or that the charge is, for example, (a) an aluminum point in an aluminous tectosilicate, (b) an aluminum removal. It is defined as being distributed over a larger molecular volume than the charge distribution at the resulting hydroxyl points.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a method for derivatizing tectosilicate according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophobic substance of the present invention is prepared by reacting a lattice silyl hydroxyl group, preferably one in a tetra-coordinated "nest" configuration to react a hydroxyl nest with an organic moiety, preferably acyl, alkyl or It is produced by substitution with a silyl group. A preferred silyl group is represented by the general formula Si (R ′) _n X _p (where n is 0 to 3, p is (3)-(n), and R ′ is aryl, alkyl, acyl, aralkyl, Selected from the group consisting of cycloalkyl and mixtures thereof, and X is a halogen or alkoxyl group). Preferred acyl, alkoxy and alkyl groups are lower acyl, alkoxy or alkyl groups such as C ₁ -C ₄ alkyl,
Alkoxy or acyl groups (both branched and straight chain)
Is. Preferably n is 1-2 and X is chloro.

The tectosilicate thus derivatized is first dealuminated, preferably by treatment with aqueous mineral acid, to form the required reaction sites within the siliceous lattice.
They are then dehydrated to expose these reactive sites. All tectosilicates may contain some incidental structural hydroxyl groups (OH), but enough hydroxyl groups to allow chemical derivatization to the extent necessary to impart useful hydrophobicity are: not exist. Therefore, the substrate tectosilicate must first be treated to increase the number of lattice hydroxyl groups and then dehydrated to form hydroxyl groups effective for subsequent chemical derivatization.

The general reaction equation of the method of the present invention can be illustrated as shown in FIG. Substitution of the (M +) metal cation of tectosilicate with hydronium ion is readily accomplished by exposure of tectosilicate to aqueous acid. As shown in FIG. 1, the Si-O-Al bond of starting material I readily protonates and dissociates to give aluminum-associated hydroxyl points in the lattice as shown by structure II. Kell (U.S. Pat. No. 3,682,996), the silylation of type II points, i.e. trimethylsilane (HSi _{(CH 3) 3)} to form the silylated aluminum-containing materials of structure III by exposure to Is disclosed. Kell disclosed that Type III silylated zeolites absorb about 40% less cyclohexane, n-hexane and water than Type II parent "hydrogen" zeolites.
However, Kell has not reported changes in selectivity preference.

Aluminous tectosilicates with a silicon to aluminum ratio (Si: Al) greater than about 5 can be dealuminated almost completely without loss of lattice integrity. R.
M. Burrer and M.M. B. McKee, Can. J. C
hem. , 42 , 1481 (1964). This has been achieved by long-term treatment of aluminous tectosilicates with aqueous acid. Dealumination structure
It is believed to give a tectosilicate with a tetra-coordinated hydroxylated nest consisting of 4 association = Si—OH moieties as illustrated in IV. These aluminum-free points may be referred to as "exo-aluminum points."

The active tectosilicate material of both structures II and IV is
It would be expected to show reduced hydrophilicity due to the absolute phenomenon of the lattice charge for aluminum removal, but with hydrogen atoms associated with the remaining aluminum atoms and / or hydrogen to free silyl hydroxyl groups (SiOH). It would be expected that the binding would still sorb water. Heating the aluminum-containing or dealuminated tectosilicate at a relatively low temperature, ie, in the presence of a vacuum, preferably at about 100-200 ° C., removes the water of hydration from the pores and the absorption pores and Clear the channel. Exposure of dealuminated tectosilicates to elevated temperatures, ie about 400-500 ° C, results in either partial or total destruction of the hydroxyl nests by dehydroxylation and formation of new Si-O-Si bonds. N. Y. Chen is J. Phys. Chem. , 8
Si greater than 80 at 0 , 60 (1976):
It is reported that dealuminated mordenite with Al ratio will not absorb water vapor at pressures of 1 or 12 mm Hg.

Earlier attempts to replace the lattice aluminum with silicon by the reaction of nests with silanes were unsuccessful. It also reports the prospect of some nested silylation to produce tectosilicates of structure V (R = SiH ₃ , x <4). M. Burrer and J. C. Trombe, J.
C. S. Faraday I 74 . 1871 (197)
See 8). They also reported that the nested hydroxyl groups appear to be less reactive to silylation than the hydroxyl groups present in structure II of Figure 1. The hydrophilicity of silylated tectosilicate was not measured.

Aluminous tectosilicates utilized as starting materials in the present invention can include crystalline, amorphous and mixed crystalline amorphous tectosilicates of natural or synthetic origin or mixtures thereof. The water-insoluble crystalline tectosilicates useful in the present invention are those with the narrowest spaced channels of about 3 to 13Å in diameter. Hereinafter, this diameter will be referred to as the pore size. The preferred pore size that characterizes the derivatized matrix materials useful in the present invention is about 3-10Å, most preferably 4-8Å. The pore size of a given tectosilicate should be large enough to accommodate derivatizing agents such as silanes, alcohols, etc., but is not desirable for undesired liquid or gas stream components, such as aromatic compounds, ketones, heterocyclic compounds, etc. It must be small enough to prevent introduction. Tectosilicates with pore sizes in the range of about 4 to 13Å are small gaseous elements and compounds such as water (kinetic diameter [σ] 2.65Å), carbon monoxide (σ).
= 3.76Å), carbon dioxide (σ = 3.30Å) and ammonia (σ = 2.60Å) are easily added.

Most usefully, the aluminous tectosilicate starting material will preferably have a lattice silicon to aluminum ratio of greater than about 5: 1. Tectosilicates having a silicon to aluminum ratio of less than about 5 tend to lose their structural integrity during dealumination.

A particularly preferred type of aluminous tectosilicate starting material is naturally occurring clinoptilolite. These minerals typically have a unit cell structure of Na ₆ [(AlO ₂ ) ₆ (SiO ₂ ) ₃₀ ] .24H ₂
O, where the sodium ion content (Na +) may be partially replaced by calcium, potassium and / or magnesium and the like. The silicon aluminum ratio in the preferred variant is
Greater than 5 and most preferably greater than about 8. The pore size is in the range of about 4.0-6.0Å. Clinoptilolite is stable to about 700 ° C. in air and maintains its structural integrity during dealumination.

Other naturally occurring aluminous tectosilicates that are useful as starting materials typically have unit cell composition Na ₈ [(AlO ₂ ) ₈ (SiO ₂ ) ₄₀ ] .24H ₂
Is a mordenite with O 2 (wherein the calcium and potassium cations can replace some of the sodium cations). Pore size is about 3.5-4.5
It is within the range of Å. The silicon to aluminum ratio is generally greater than 5.0 and can be greater than 10 in some samples. Other aluminous tectosilicates, such as ferrierite or erionite, will also usefully provide the starting material.

Although naturally occurring aluminous tectosilicates are preferred starting materials because of their low cost and high availability, synthetic analogs of natural tectosilicates and their derivatives have equivalent utility in this method. Let's do it. For example, synthetic mordenite, available from Norton Company (registered trademark Zeolon).
Would be an acceptable starting material for use in the present invention. Also, other synthetic porous tectosilicates that are not homogenous in nature could serve as acceptable starting materials.

The formation of the hydrophobic substance of the present invention generally proceeds in three steps: (1) dealumination, (2) dehydration and (3) derivatization with a suitable alkylation, acylation or silylating agent. Let's do it.

Dealumination of aluminous tectosilicates with acids is well known in the art. For example, R. M. Burrer and M.M. B. McKee, Canadian J. Che
m. , 42 , 1482 (1964) reported complete dealumination of clinoptilolite by refluxing the sample in different concentrations of aqueous hydrochloric acid. In this method, a strong acid treatment comprising refluxing, ie, exposing the sieved, finely divided aluminous tectosilicate to boiling 2-10N aqueous mineral acid for about 1-3 hours,
preferable. Although other acids, such as sulfuric acid, nitric acid or phosphoric acid may be useful in some cases, the preferred acid is 3
~ 7N hydrochloric acid.

In some cases, mild acid treatments involving percolation of aqueous acid through a column of crushed aluminous tectosilicate under ambient conditions have been found to be satisfactory. Preferably, the tectosilicate starting material is about 2
Si: Al ratios greater than 5, preferably dealuminated to ratios greater than 100, for example ratios of about 150-300, and under most preferred conditions essentially any lattice as measured by X-ray fluorescence. Aluminum will not be retained either.

The dealuminated air-dried tectosilicate material is then heated to remove most of the water of hydration of the pores and expose the remaining lattice hydroxyl groups to derivatization. The heating can be carried out at a temperature sufficient to effect substantial dehydration without significant lattice dislocation and subsequent loss of reactive sites. Typically, the dealuminated material is heated to about 100-200 ° C., preferably under reduced pressure for about 10-40 hours. Studies of the effect of elevated temperatures, ie 500-600 ° C., on tectosilicates that have been subjected to acid treatment at ambient temperature showed that the samples showed substantial hydrophobicity compared to the starting material, but derivatization did not It was shown that there was no further increase.

After thermal dehydration at low temperature, eg, about 100-200 ° C, the dealumination dehydrated material is allowed to cool and then exposed to a derivatizing reagent. The derivatizing reagent reacts to functionalize the internal lattice silyl-hydroxyl groups, the majority of which are believed to reside in the tetra-coordinating nest of unit structure IV as illustrated in FIG. After exposing the aluminium-free point (“exoaluminum point”) to the derivatizing reagent, the nest point is about 1 to 4 [Si—OR] units, where R is 1 to 3 halogen, alkoxyalkyl, Aryl, aralkyl, or alkyl substituted with a cycloalkyl substituent, acyl, or silyl,
And an alkyl, alkoxy or acyl group, either directly attached to the lattice silyloxy or attached to the silicon atom of the R group, is preferably a C ₁ -C ₄ alkyl, alkoxy or acyl group). Ah

Nestsilyl-Reagents useful for replacing hydrogen atoms of hydroxyl groups with substituents R (RX) are a wide variety of reagents known in organic chemistry to be useful for alkylating, acylating or silylating hydroxyl groups. Includes. Such agents are commonly known as I.V. T. Compend by Harrison and others
ium of Organic Synthetic
Methods , Willie Interscience , New York (1971), pages 124-131. That disclosure is incorporated herein by reference. Preferred reagents are lower C _{1 to} C ₄ alkanols or C ₁ to
C ₄ alkyl halides include, for example, methanol, ethanol and the like or methyl chloride, methyl iodide, ethyl chloride, butyl bromide and the like. Lower C ₁ -C ₄ alkanols have been found to be particularly effective as derivatizing agents when thermally reacted with tectosilicates under pressure either neat or in the presence of a catalyst. . Other useful alkylating reagents _include the C 1 -C ₄ diazoalkane.

Nested hydroxyl groups can be acylated by exposure to ketene, such as ketene itself or alkyl or dialkyl ketene, such as dimethyl ketene. Reaction of the silyl-hydroxyl group with a ketone gives the SiOR moiety, where R is acetyl, while reaction with dimethylketene introduces R as dimethylacetyl.

Various silylating reagents can be used to introduce substituted silyl substituents into the tectosilicate nest, ie, R can be [Si
(R ′) _n X _p ] (in the formula, n is 0 to 3, p is (3)-(n), and R ′ is C _{1 to} C ₄ lower alkyl, C _{5 to} C ₇ cycloalkyl. , Aryl, C ₁ -C ₄
Selected from the group consisting of acyl, aralkyl and mixtures thereof; and X is a halogen atom, ie Cl, F,
I, Br or a mixture thereof, or a lower alkoxy group).

In addition, the di-, tri- or tetra-functional silylating reagent reacts with 2 to 4 = Si-OH groups in a single nest to eliminate aluminum atoms that disappear, as a bridging unit SiR'q (wherein q is 0. ~
2) and can thus be crosslinked at one or two silicon atoms at the aluminum deficiency point. This reaction involves elimination of 2-4 HX groups and O-
It will be caused by the formation of Si-O bridges. For example, dimethyldichlorosilane is a lattice Can be done. Of course, the methyl group can be replaced by any of the groups represented by R'and Cl can be replaced by another halogen atom or by an alkoxy group.

Typical monofunctional silylating reagents that introduce Si (R ′) ₃ units include trimethylchlorosilane, trimethylfluorosilane, dimethylisopropylchlorosilane, and the like. Preferred bifunctional silylating agents include dihalodialkylsilanes such as dichlorodimethylsilane and dialkoxy (dialkyl) silanes such as diethoxydimethylsilane. Tri- and tetrafunctional silanes such as silicon tetrafluoride, tetrachlorosilane, and trifluoromethylsilane can also be used to derivatize the tectosilicates of the present invention.

The reaction between the dealumination dehydrated tectosilicate and the silylated reagent can be carried out by contacting the substance with the reagent in a liquid phase or a gas phase. Preferably, excess silylating reagent in a suitable solvent is slurried with tectosilicate. Heating and / or addition catalysts can be used if desired depending on the reactivity of the tectosilicate and silane.

Gaseous hexamethyldisilazane is used in An
al. Chem. 48 , 2289 (1976) to react with a lattice hydroxyl group to introduce a trimethylsilyl group into a nest. The disclosure of which is incorporated herein by reference.

The method of the present invention readily provides a hydrophobic microporous crystalline siliceous material that exhibits a greatly reduced affinity for water while maintaining a high affinity for low polar molecules such as ammonia. The decrease in hydrophobicity or hydrophilicity of tectosilicate can be quantified by the absorption of water per unit (retention volume) of tectosilicate under a given set of exposure conditions. The observed decrease in water retention, as opposed to general retention, is due to hydrophobicity, which measures retention of comparable-sized molecules of comparable or low polarity, such as ammonia, nitrogen, methane, or carbon dioxide. Can be established by doing. Through the use of these general techniques, the derivatization method of the present invention provides a better absorption capacity than that observed prior to the derivatization step but after the tectosilicate is acid treated and activated for derivatization by heating. Additional 10-50
%, Preferably about 15-45%, to give a microporous crystalline siliceous material exhibiting an affinity for vapor [as measured by retention (H ₂ O ml / g material) at STP]. When ammonia vapor retention is used as a reference, the absorption of water vapor into the derivatizing material is no more than about 20-80% of the absorption of ammonia and is probably much less. In contrast, both ammonia and water show a retention volume of greater than 200 ml of vapor per column-g of aluminous tectosilicate under the gas-solid chromatography conditions used to measure the retention volume. Acid-treated or non-derivatized heat dehydration or non-derivatized heat dehydration or hydration irreversibly absorbed on the tectosilicate sample.

The invention will be further illustrated by reference to the following examples.

The following six methods have been used to modify the properties of clinoptilolite (Hector, Cal., NL).
Industries).

Method A1-Mild Acid Wash Tectosilicate, clinoptilolite, was crushed in a Jaw crusher and then milled in a Brown mill. The mill grind is passed through a 50-100 mesh® RoTap sieve agitator and a 2 / diameter 3 foot long Pyrex tube of 2 cm diameter is used.
Used to fill 3. The powdered material was held in place with a glass wool plug. Hydrochloric acid (6N) 40 to 27
Flush the packed column at a rate of about 9 ml / min at ° C.
The acid treated material was washed by flushing with 3 column volumes of distilled water and then air dried. Clinoptilolite (Hector, Ca treated in this way
l. ) Is light green and indicates a Si: Al ratio of about 30.

Method A2-Strong Acid Wash 4. Add the light green material (225 g) isolated from Method A1.
0 round bottom flask and 6N HCl 2.0
Was added. The slurry was heated under reflux for 2.0 hours. The white mineral was collected by vacuum filtration and washed repeatedly with deionized water. The Si: Al ratio of the clinoptilolite thus treated was about 212.

Method H1-mild heat treatment Finely ground tectosilicate (clinoptilolite) about 10
g was placed in a 250 ml beaker and heated in a vacuum oven at <10 mm Hg to 150 ° C for 20 hours.
After heating in vacuo, the material was stored at 150 ° C at ambient pressure.

Method H2-High heat treatment Finely ground tectosilicate (clinoptilolite) about 10
Add g to a 250 ml beaker made of quartz and 550
Heat at ambient temperature for 14 hours at ° C, then 150
Transferred to a ° C oven and stored at ambient pressure.

Method D1-Silylation Pyridine was left on potassium hydroxide pellets for 24 hours, then distilled from barium oxide and stored on 4Å molecular sieves. Toluene was refluxed over sodium metal for 3 days, then distilled, and Linde type 4Å
Stored on molecular sieve. A reagent mixture of 20% pyridine, 15% dichlorodimethylsilane and 65% toluene was prepared and stored on a molecular sieve.

2 with magnetic stirrer, reflux condenser, and argon inlet
Flush a 50 ml round bottom flask with dry argon,
Then, 10 g of finely ground tectosilicate was charged, and then 100 ml of the reagent mixture was added. The resulting slurry was refluxed for 20 hours. After the reaction, the acid-treated tectosilicate material was isolated by filtration and washed with dry toluene, methanol. Substance in methanol at least 2
Reflux for hours, collect by filtration, and store under ambient conditions.

Method D2-Methylation About 5.0 g of the finely ground material was placed in a steel bomb containing about 50 ml of methanol. The cylinder is sealed and the temperature is 4 to 12 at 220 ° C.
Heated for hours. The bomb was cooled to 25 ° C and the material was collected by filtration.

Gas Retention Volume Measurement The treated finely ground tectosilicate was vacuum packed into a silylated glass column (0.125 inch id, 0.25 inch id) and held by a plug of silylated glass wool. The column was inserted into the furnace of the gas chromatograph. Maintain the inlet at 200 ° C and the detection furnace at 250 ° C.
And the column was maintained at an initial conditioning temperature of 45-50 ° C for 10-30 minutes. The sensing filament current was kept at 150 mA and the carrier gas (He) inlet pressure was 60 psi. Gas injection (7
5-125 μl was performed at a pressure 4-7 psi above ambient pressure and the liquid injection had 1-2 μl.
The water and ammonia retention volumes were measured at a column temperature of 200 ° C. Under these conditions, ammonia was irreversibly absorbed. The result was expressed as K (absorption gas in STP ml absorbent g).

Properties of multi-stage modified Hector California clinoptilolite prepared by various combinations of the above methods are summarized in Table I. In all cases, the methods were performed in the order shown or omitted. The silicon: aluminum ratio was measured by energy dispersive X-ray spectroscopy (tracor spectacles model 440, tracor nazan 2000 analyzer) and reduction of data was achieved using Program Super ML (tracor x-ray incorporated). .

1 STP ml / g; K (NH ₃ ) is in all cases>
It was 200.

2 Lattice Al was not detected in these materials.

3 Anomalous results are probably due to operational error.

4 Galbraith Laboratories, Knoxville, TN, Inc. From the results presented in Table I, the combination of mild acid or strong acid cleaning followed by high or low temperature heating showed that the tectosilicate was hydrophobic even without further derivatization steps. It is generally found to significantly increase the sex. The effect is most pronounced in the case of the sample (A ₂ H ₁ D. Example 4) which was washed with strong acid and then heated at 150 ° C. However, Examples 3 and 2
We demonstrate that a further significant increase in hydrophobicity can be achieved by silylation or methylation of this material, respectively. The total carbon% is also 400 in each case for these substances.
It is increased by more than%. Similarly, an increase in hydrophobicity is observed in the case of silylation (Example 8) or methylation (Example 5) of the material of Example 9 which has been subjected to a mild acid wash and then to heating at 150 ° C. . The greater affinity for water observed with these materials as opposed to the materials of Examples 3 and 2 reflects the presence of more reactive points, the silyl nests, in the two materials exposed to the stronger dealumination conditions. It is thought that.

However, Examples 7 and 13 show that no increase in hydrophobicity was observed with the substance of Example 6 when derivatization was attempted, rather a decrease was observed. The derivatization failure affecting hydrophobicity observed with the material of Example 6 is believed to be due to the breakdown of the hydroxynests or other reactive sites formed by the initial acid wash. Furthermore, comparisons with Examples 8 and 7 and comparisons with 9 and 6 show that in the case of otherwise equivalently prepared samples, the high heat treatment (H2) attempted either methylation or silylation. It is shown to sometimes result in significantly lower carbon loadings. This provides yet another support for a mechanism involving the production and storage of active nests according to a strong acid-mild heat treatment combination. Attempted silylation of the acid-washed but not dehydrated (by heating) material (Example 12) failed to increase the hydrophobicity of the material of Example 11, possibly due to blockage of the reaction site by water of hydration. It was Methylation of the same material resulted in a median increase in hydrophobicity (Example 10).

The hydrophobic derivatizers of Examples 3 and 2 also have no lattice aluminum detectable by fluoroscopy and negative results are expected and observed in the case of the registered mark Silicalite (Union Carbide). Was done. This provides confirmation that the strong acid wash conditions are effective in removing lattice aluminum and producing a reactive hydroxyl containing nest that is effective for derivatization. Removal of the lattice aluminum is adequate by itself to significantly increase the hydrophobicity of clinoptilolite, and, in fact, is the major contributor to the included hydrophobicity, but is not the case in Examples 8, 3, 5 and From 2,
It is clear that the hydrophobicity is optimized by further silylation or methylation in the case of this example process variable. Significant hydrophobic effects are commonly observed in both derivatized and derivatized materials when the Si: Al ratio exceeds about 25.

INDUSTRIAL APPLICABILITY Hydrophobic substances prepared according to Examples 8, 3, 5 and 2 absorb significant amounts of ammonia from human or animal moist excretion and are not used with previously used substances such as derivatized substances. It would be expected to absorb more effectively than tectosilicates, phyllosilicate clays, silica gels and the like.
To this end, the novel materials can be incorporated into diapers, padding, etc. either in a vapor or moisture permeable compartment or distributed throughout the fabric matrix. For example, in the case of a bed pad or disposable diaper, which typically consists of an absorbent core of natural or synthetic fibers, a permeable top or inner sheet and a liquid impermeable back or outer sheet, an effective amount of the novel material of the present invention. Can be incorporated into the absorbent core of a disposable diaper. The amount of ammonia absorbent used is about 1% to about whether the diaper is intended for day or night use; depending on the age of the user.
It can vary from 50%, preferably about 15% to 25% (based on the weight of the diaper). Additionally, an effective amount of the novel material can be solution coated onto the topsheet of a disposable diaper and incorporated into the absorbent lining of plastic baby pants or into a fabric diaper (technically to disperse particulate solids into a fibrous substrate. By known methods).

The novel hydrophobic materials of the present invention may also be used as animal litter, preferably when agglomerated into pellets, either alone or in combination with other absorbent materials. Typical animal litters consist of absorbable inorganic or organic materials such as attapulgite, birch mullite and calcium montmorillonite (ie clay), agglomerated wool dust, wool chips, dehydrated grass, straw, or alfalfa, fly ash, etc. . An effective amount of the novel substance, for example about 5 to 95%, preferably about 20% to 30
% Or higher (based on the total weight of the litter) to these litters will enhance the deodorizing ability of the litter without substantially reducing the absorbent properties of the litter.

In addition, the novel hydrophobic substance of the present invention, pipe, cigar,
Alternatively, it can be used either in a filter cartridge in a cigarette, either alone or dispersed and / or deposited over conventional tobacco smoke over material. When used in this capacity, an effective amount of the novel hydrophobic material is a more effective and significant amount than the hydrophilic materials commonly used in smoke filters, such as cellulose, activated carbon, naturally occurring or synthetic aluminous tectosilicates. It would be expected to absorb carbon monoxide from mainstream smoke. For example, a filter can be made with a section consisting of about 10-75 mg of novel hydrophobic material, preferably about 40-50 mg, either on the front or the back of the standard filter material. In addition, about 10-40m of new material
g, preferably about 20-30 mg, may be incorporated into the standard filter material itself. Similarly, an effective amount of a pulverulent material of the present invention is a packaging material used to shape a cigarette or cigar to reduce carbon monoxide in the sidestream smoke of a burning cigar or cigarette, such as paper and tobacco. Could be blended into. The amount used is the total weight of the packaging material used,
It will depend on volume and composition.

While certain representative embodiments of the present invention have been described herein for purposes of illustration, it will be apparent to those skilled in the art that modifications may be made without departing from the spirit and scope of the invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area A61F 13/15 B01J 20/10 C 7202-4G 29/04 M 9343-4G C07F 7/02 C 8018 -4H

Claims (25)

[Claims] 1. A formula Including an aluminium-free point in the siliceous lattice, characterized by the presence of about 1 to 4 associated moieties in which R is a substituent that is a weaker point source than aluminum.
Hydrophobic microporous crystalline tectosilicate material with regular geometric shape. 2. The substance according to claim 1, wherein R is a substituent which is a point power source weaker than a hydroxyl group. 3. R is C ₁ -C ₄ alkyl, C ₁ -C ₄ acyl, and SiR ′ _n X _p (wherein R ′ is C ₁ -C _4).
Selected from the group consisting of alkyl, cycloalkyl, aryl, C ₁ -C ₄ acyl, aralkyl and mixtures thereof, X is a halogen atom or a lower alkoxy group, n is 0-3 and p is (3 )-(N)) The substance of claim 2 which is a substituent selected from the group consisting of: 4. An aluminium-free point is a unit SiR ′ _q (wherein q is 0 to 2, and R ′ is C ₁ -C ₄ alkyl, cycloalkyl, aryl, C ₁ -C ₄ acyl, aralkyl. And the material of claim 2 which is crosslinked by 1 to 2 (selected from the group consisting of: and mixtures thereof). 5. A material according to claim 3 or 4, wherein said dots are made by a method comprising removing aluminum from an aluminous tectosilicate lattice. 6. R is C ₁ -C ₄ lower alkyl or Si
R _'n Cl (wherein, R' is _C 1 -C ₄ alkyl,
And n is 1 to 2). 7. The material of claim 5 wherein the lattice Si: Al ratio after aluminum removal is greater than about 25. 8. The material of claim 7 wherein the lattice is essentially aluminum free. 9. A material according to claim 1 which exhibits an absorption of water vapor which is not more than about 20-80% of the absorption of ammonia vapor. 10. (a) Aluminum deficiency points are created in the lattice of a natural or synthetic aluminous tectosilicate starting material (said points are Characterized by the presence of about 4 parts), (b) heating the aluminum-deficient tectosilicate to remove water of hydration, Reacting the moieties with a derivatizing reagent, whereby about 1 to 4 of said moieties per point are (Wherein R is a substituent which is a weaker point power source than aluminum) and is converted to a portion thereof. A method for producing a hydrophobic crystalline substance having a regular geometric shape, comprising: 11. R is C ₁ -C ₄ alkyl, C ₁ -C ₄
Acyl and SiR ' _n X _p , wherein R'is selected from the group consisting of cycloalkyl, aryl, acyl, alkyl, aralkyl and mixtures thereof, X is halo or lower alkoxy and n is 0-2. Yes, and p
Is a substituent selected from the group consisting of (3)-(n)), or 2 to 4 of the Si-OH moieties are units S.
iR _'q (wherein, q is 0-2) is crosslinked by the method of paragraph 10 claims. 12. = reaction between two and derivatization reagent Si-OH moiety, desorption and units of two HX portion -SiR ₂
12. The method of claim 11 which results in crosslinking of the moieties by-. 13. R is C ₁ -C ₄ , or R ′ is C
A ₁ -C ₄ alkyl, n is 1-2, and X
The method of claim 11 wherein is chloro. 14. The method of claim 10 wherein the starting material has a Si: Al ratio of greater than about 5: 1. 15. The method of claim 11 wherein the aluminum deficiency points are created by exposing the aluminous tectosilicate to an aqueous mineral acid. 16. Substantially all of the aluminum is removed from the aluminous tectosilicate lattice.
Method of paragraph 5. 17. (a) A substantial portion of aluminum is removed from the lattice points of the alumina-based tectosilicate, Creating an aluminum deficiency point characterized by about 4 parts, (b) dehydrating the aluminum deficiency tectosilicate at a temperature at which the integrity of the lattice is retained, and at temperature; The moiety is reacted with a derivatizing reagent selected from the group consisting of dihalodialkylsilanes, dialkoxydialkylsilanes, C ₁ -C ₄ alkanols and C ₁ -C ₄ alkyl halides, whereby about 1 to about 1 of said moieties per point is obtained. Formula 4 [Wherein R is selected from the group consisting of C ₁ -C ₄ alkyl or SiR ₂ X, where X is a halogen atom], or at least two per point A method for reducing the hydrophilicity of tectosilicates, characterized in that the moieties are crosslinked by the unit SiR'q, where q is 0-2. 18. The method according to claim 17, wherein the derivatizing agent is dichlorodimethylsilane or methanol. 19. The method according to claim 17, wherein the starting material is clinoptilolite. 20. Including an aluminium-free point in the siliceous lattice, characterized by the presence of about 1 to 4 associated moieties in which R is a substituent that is a weaker point source than aluminum.
A diaper comprising an absorbent inner core containing an effective amount of a regular geometrically shaped hydrophobic microporous crystalline tectosilicate material. 21. Including an aluminium-free point in the siliceous lattice, characterized by the presence of about 1 to 4 associated moieties in which R is a substituent that is a weaker point source than aluminum.
A bed pad comprising an absorbent inner core containing an effective amount of a regular geometrically shaped hydrophobic microporous crystalline tectosilicate material. 22. Including an aluminium-free point in the siliceous lattice, characterized by the presence of about 1 to 4 associated moieties in which R is a substituent that is a weaker point source than aluminum.
Animal litter comprising an effective amount of a regular geometrically shaped hydrophobic microporous crystalline tectosilicate material. 23. Including an aluminium-free point in the siliceous lattice, characterized by the presence of about 1 to 4 associated moieties in which R is a substituent that is a weaker point source than aluminum.
A cigarette or pipe filter, characterized in that it contains a hydrophobic microporous crystalline tectosilicate material of regular geometric shape. 24. The filter according to claim 23, which contains about 40 to 50 mg of a hydrophobic substance. 25. Including an aluminium-free point in the siliceous lattice, characterized by the presence of about 1 to 4 associated moieties in which R is a substituent that is a weaker point source than aluminum.
A cigarette or cigar package, characterized in that it contains a regular geometrically shaped hydrophobic microporous crystalline tectosilicate material.